FI86640B - 3-ALCOXI-2-HYDROXIPROPYLDERIVAT AV CELLULOSA SAMT ANVAENDNING AV DESAMMA I BYGGNADSMATERIALKOMPOSITIONER. - Google Patents

Abstract

Water-soluble cellulose ether derivatives being a substituent selected from the group consisting of hydroxyethyl, hydroxypropyl, and methyl and also substituted by about 0.05 to about 50% of a 3-alkoxy-2-hydroxypropyl group in which the alkyl moiety is a straight or branched chain alkyl group having 2 to 8 carbon atoms, and building compositions containing the said derivatives and a hydraulic or synthetic binder are disclosed.

Description

86640

CELLULOSE 3-ALCOXY-2-HYDROXYPROPYL DERIVATIVES AND THEIR USE CONSTRUCTED IN MATERIAL MIXTURES - 3-ALCOXY-2-HYDROXIPROPYLDERIVAT AV CELLULOSA SAMT ANVÄNDMA AV DE-SAMT

The invention relates to water-soluble cellulose ether derivatives and their use in building material mixtures.

Water-soluble cellulose ethers, such as hydroxyethylcellulose, hydroxypropylcellulose and methylcellulose, are well known as additives in building material mixtures or building materials such as concrete, tile mortars and tile adhesives, ready-to-use plasters, cementitious plasters, projection plasters mortars to be applied, underwater concrete, grouts and grouts, crack fillers, floor screeds and fixing mortars.

These compositions are essentially Portland cement, building gypsum or vinyl copolymers and contain functional additives that provide the specific properties required in various building applications. The water content of such mixtures, i.e. the so-called the control of the "water ratio" is important when the physical properties of the mixtures, such as formability, consistency, "open time", i.e. the time during which the wet product remains moldable, tack, water separation, surface adhesion, setting time and air retention, are desired at the desired application level. .

For this purpose, non-ionized cellulose ethers are preferred additives.

Commercially available non-ionized, water-soluble cellulose ethers of a nature

2 S 6 6 4 O

hydrophobic, are the most widely used because they have the most beneficial effect on consistency and open time, i.e. the time during which the wet product remains usable or moldable. However, none of these cellulose ether derivatives provide all of the most preferred combinations of properties for building material blends.

Hydroxyethylcellulose (HEC) is the most hydrophilic non-ionized water-soluble cellulose ether and provides good water retention and moldability, but pastes made from HEC still tend to run down the surface.

The more hydrophobic methylcellulose (MC) retains air in the paste when mixed with water and results in a less dense paste with good consistency and open time. The less pseudoplastic behavior of this cellulose ether provides pastes that are better able to resist gravity runoff, but the formability of such pastes is not as good as that made with HEC. Another disadvantage of MC is its reduced solubility at elevated temperatures, which can cause consistency problems in warm air.

Due to these shortcomings, attempts have been made to convert MC to hydrophilic groups and HEC to hydrophobic groups. However, the addition of hydrophilic groups such as hydroxyethyl and hydroxypropyl does not significantly improve the performance of conventional MC products, nor does the addition of non-hydrophobic groups such as benzyl, phenyl and hydroxypropyl improve the performance of HEC. Nor can such a modified HEC be prepared economically or by conversion with long chain alkyl groups, as Landoll has described in U.S. Pat. 4,228,277 and 4,352,916, give better performance than hydroxypropyl modified HEC.

3 S 6 6 4 G

E. D. Klug describes in Some Properties of Water-Soluble Hydroxyalkyl Celluloses and Their Derivatives, 36 Journal of Polymer Science, Part C 491-508, 497-98 (John Wiley & Sons, Inc. 1971) the use of a long chain glycidyl ether such as decylglycidyl ether -oxypropylcellulose and hydroxyethylcellulose, but these long chain substituents do not give the desired results when used in building material mixtures.

Additives would be needed for building material mixtures that would provide better combinations of properties such as water retention, formability, consistency, appearance, open time, air content, and adhesion, but would not bring with them the aforementioned disadvantages of HEC and MC.

The present invention provides a water-soluble cellulose ether derivative having a first substituent selected from the group consisting of hydroxyethyl, hydroxypropyl and methyl, and the derivative is characterized in that it is also substituted with about 0.05 to about 50% of substituted based on the mass of the cellulose ether derivative, a 3-alkoxy-2-hydroxypropyl group whose alkyl moiety is a straight-chain or branched alkyl group having 2 to 8 carbon atoms.

The cellulose ether derivatives according to the invention are practically completely soluble in water at ambient temperature. They can be prepared as described below from any conventional cellulose ether derivative having a sufficiently accessible reactive hydroxyl group, such as hydroxyethylcellulose (HEC) or directly from pure cotton or any other conventional cellulose source.

4,86640

Among the polymers from which cellulose derivatives can be prepared, e.g. hydroxyethylcellulose (HEC), hydroxypropylcellulose (HPC), methylcellulose, hydroxypropylmethylcellulose (HPMC) (also known as methylhydroxypropylcellulose), methylhydroxyethylcellulose, hydroxyethylcellulose, ethylhydroxyethylcellulose, hydroxypropyl

Commercially available materials that can be used to make the polymers of the invention include e.g. Natrosol and Klucel (Aqualon Company, Wilmington, DE), Culminal (Aqualon Company and Aqualon GmbH & Co. KG, Diisseldorf, Federal Republic of Germany), Blanose (Aqualon France BV,

Alizay, France) and Methocel (Dow Chemical Comapny,

Midland, MI).

The preferred first substituent of the cellulose ether derivatives is hydroxyethylhydroxypropyl and preferably hydroxyethyl and the cellulose ether derivative is non-ionic and has a molar degree of hydroxyethyl substitution (MS = molar amount of substituent per cellulose anhydro-glucose unit of about 1.5). Preferably, the polymer has a degree of polymerization of about 1500 to about 4000.

The 3-alkoxy-2-hydroxypropyl group is preferably present in an amount of from about 0.05% to about 50% by weight, more preferably from about 0.1% to about 25% by weight based on the dry weight of the substituted polymer. Preferably it is a straight chain alkyl group having 2 to 6 carbon atoms. Such groups include e.g. ethyl, propyl, butyl, pentyl and 2-ethylhexyl. Most preferred is an n-butyl group.

s 86640

The alkylglycidyl-derived radical-containing polymers of the invention can be prepared by suspending a polymer such as HEC, HPC, HPMC, etc. in an inert organic diluent such as a lower aliphatic alcohol, ketone or hydrocarbon, and adding an alkali metal hydroxide solution to the resulting suspension at low temperature. After the alkali has wetted and swelled the ether thoroughly, the alkyl glycidyl ether is added and continued with stirring and heating until the reaction is complete. The remaining alkali is then neutralized and the product is collected, washed with inert diluents and dried. This method is well known in the art, for example, from U.S. Patent Nos. 4,228,277 and 4,352,916.

The polymers of the invention can also be prepared directly from cellulose. For example, alkyl glycidyl-modified HEC can be prepared by first adding pure cotton to a mixture of an inert organic diluent and an alkali metal hydroxide. Ethylene oxide is then added to the alkalized cellulose thus obtained, and the product obtained is treated with nitric acid. Alkyl glycidyl ether is then added to the reaction mixture thus obtained and, if desired, another ethylene oxide treatment is carried out. When the reaction is complete, the product is neutralized, filtered, washed with aqueous, inert solvents and dried.

The building material mixture containing a hydraulic or synthetic binder according to the invention is characterized in that it also contains from about 0.5% to about 5% by weight of the water-soluble cellulose ether derivative according to the invention.

The preparation of the polymers of this invention is illustrated by the following examples. All parts and percentages are by weight unless otherwise indicated.

Preparation Example 1

A suspension was prepared of 80 parts by weight of high viscosity hydroxyethylcellulose (MS 2.5; viscosity of a 1% solution measured on a Brookfield LVF viscometer 3400 mPas) in tert-butanol (859 parts) and water (113.4 parts). part) in the mixture. The suspension was degassed by Ν -, - purging. To the suspension thus obtained was added 2.6 parts of a 50% aqueous solution of NaOH. The temperature of the suspension was maintained at ambient temperature by removing the heat generated due to the addition of sodium hydroxide. The suspension was stirred under nitrogen for 45 minutes. Then 24 parts of n-butyl glycidyl ether were added. The temperature was raised to 90 ° C per hour and held for two hours. The mixture was then cooled to 25 ° C and neutralized with 65% aqueous nitric acid. The reaction liquid was removed and the product was washed and cured with acetone / water mixtures of 80/20 (twice), 84/10, 88/12, 92/8, 96/4 and 98/2.

The product was collected by filtration and dried in a fume hood for 60 minutes. The product obtained had 3-butoxy-2-hydroxypropyl-Pyli-MS of 0.35 and a cloud point of 70 ° C in water.

Preparation Example 2

A suspension of 80 parts by mass of high viscosity hydroxyethylcellulose (MS 3.2) in a mixture of pure acetone (173.2 parts) and water (15.6 parts) was prepared. The suspension was thoroughly degassed by Nj-through blowing. A solution of 3.8 parts of a 50% aqueous solution of NaOH and 0.076 parts of water was then added while cooling. The suspension was allowed to swell while stirring under nitrogen pressure for 15 minutes. 15.3 parts of n-butyl glycidyl ether were then added. The reactor was pressurized to 7 ° C and heated to 90 ° C in about an hour.

This temperature was maintained for about 4 hours. The reaction mixture was then cooled to about 40 ° C and neutralized with HNO 2 (65%) and acetic acid. The reaction liquid was removed and the remaining suspension was washed three times with 200 parts of acetone (96%), filtered and dried at 60 ° C in a fume hood. The 3-butoxy-2-hydroxypropyl-MS-MS thus obtained had 0.27 and a cloud point of 78 ° C in water.

Preparation target 3

The procedure of Example 1 was repeated, but now 20 parts of 2-ethylhexyl glycidyl ether were used instead of n-butyl glycidyl ether and the reaction was allowed to proceed for 4 hours at 75 ° C. The product thus obtained 3- (2-ethylhexoxy) -2-hydroxypropyl-MS had 0.29 and a cloud point of 74 ° C in water.

The dry matter component of building material blends into which the 3-alkoxy-2-hydroxypropyl polymers of this invention may be incorporated consists essentially of a binder and fillers. The binder may be a hydraulic binder such as Portland cement or building gypsum, a dispersion such as a vinyl acetate-ethylene copolymer dispersion, or in some cases a combination thereof. The amount of binder can be from about 2 to almost 100% by weight, i.e. not more than about 99% by weight, based on the total dry matter content of the mixture:. Examples of fillers are e.g. gravel, sand, quartz sand, dolomite, gypsum, lime, limestone and combinations thereof. If a lower weight is required, lightweight extenders such as perlite, vermiculite or polystyrene may be used. Fillers can be used up to 95% by weight of the total dry matter of the mixture. calculated on the basis of The exact ratio of filler to binder and the choice of filler will be determined by what the building material formulation B6640 in question is intended to be used for.

In addition, other additives such as binding retarders, binding accelerators, plasticizers, surfactants, defoamers, solvents, fusing agents, preservatives, inorganic and organic fibers, and water-soluble polymers such as polyacrylamides, about -% based on the total dry matter content of the mixture.

The dry phase is suspended or dispersed in water to give concrete, mortar, glue or other building material. The exact amount of water is adjusted according to the intended use. For example, concrete requires relatively large amounts of water compared to, for example, joint mortars, which must be more viscous.

Polymers with a large number of substituents, i.e., those with a high level of 3-alkoxy-2-hydroxypropyl group substitution, have a cloud point (the temperature at which a 1% solution of the polymer begins to become cloudy when heated slowly). The cloud point of a polymer indicates its hydrophobicity. A relatively low cloud point indicates greater hydrophobicity. Polymers with a lower cloud point are expected to provide relatively higher air retention and air stabilization for gypsum and cement mortars. At low levels of substitution, no cloud point occurs in water at temperatures below 100 ° C. In order to determine their hydrophobicity compared to unsubstituted products, turbidity points can be measured in saline solutions, e.g. 15% NaCl solution. The performance of products with a cloud point is particularly good in tile cement mortars and gypsum-based adhesives in water below 100 ° C. Products that do not have a cloud point in water at temperatures below 100 ° C give excellent results in projection plasters, cement block materials and cement mortars.

The present invention is illustrated by the following non-limiting examples, in which all parts, percentages, etc. are by weight and all weight percentages are based on the total weight of the solid phase of the building material mixture, unless otherwise indicated.

The cellulose ethers used in the examples are described in Table 1 below.

10 • HO G f / - S '"i SS ä 8 8 8 8 8 8 S 8 8 8 8 ho6 X -P cp ocno-Hin ^ Ln ^ rtrto

wc) IX cm-1'-1R-1R-1R-1R-1R-1R-1R

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ε E CO O tH r — I t — I

CO 0) - "" tn c a en tn

• O i — I

s

• <-1 I I I I I I I O I

(X

X

C/O

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III I I I I H H H

s c C \ J | • tn en to r-: o

• t-'OtOlOCOS’O -H

O cocoq-cAjr-toco>, 3 io * o 'o * o * o "o" o ”iii« je -μι tn 3 v- e ·· -p s-, o co ^ o -ho en e · » r · »cococ ^ otn c \ jc: co fl> · OJOO> —tC ^ COCMOCM <-H fflr-l m« CO Ή; χ · <-i co ro co cm co n ro o ι o -μ -h 2 wot, ° · e -μ oxe cj 3 TI x

1-1 O 3 CO

ή OjCOcOcOcOcOcOcO Λ -h 0 Etntotntntntntntn> m 1 8888888 3J.

. - rH <—I rH rH r — I <- | rH f

1 3333333 10 H

(0 Ή e — I rH rH r-H r-1 f — I z τΗ: 0 rH Ή r-H rH rH rH rH O £ Ό π ewwcococowwqE -p a> 5 a>

SH "· Γ“ * · ι— · · Η · γη * rt · ιΗ · ι— · Gj S (fi p fH

A r-H rH rH r-H rH rH rH 5. (n C / 3 * Cp I I lii

C OOOOOOOOMS, O 3 -P TO C

ΤΗ rH * 1— · · ι— »* H * r» * r- * * r- * »r * 'O E tH 3 3 fl} CQ

<Dwwcocqtocow ^ 'P .p .μ 5 E

E- * 3 · <1 -P ft CO

-ippppppp ^ co 3 -p -h tn en mCC.CiCC.CiC en 3 to -μ en tOOTOTOTDOOOcOQCO h .Q 0) 0 ·· • ho tn -μ p λ oo -H £ i: i: x: x: jC £ Qr-tQ en wp rt y >> Ή • f · Η · Η · γ «-it -rl O 3 Ο ä Ή W 3 tn

Ή Ή ι — I. — IrHrH. — I i-H I ι — I P ι — I * H -P CM

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1- »CCC Ci M Ci C (0 rH CO>) C · Ρ g · Η 1) co αο.ααααα · π >> h -p ci we« -nq ^ · γ * · γ · · Η · π * Η · Η · Η H ^ *> rH Q) ιΗ Cy Q · -Ρ 11251355¾ U22222223S.S f 23 * «3 £ Ό Ό Ό Ό Ό Ό Ό · η -ri · η C Ό 3 C» 1 Μ • η >>: >>>>>, >>>>>, «) to ο) Ό>» -Ρ Ό ο) · η >> χ: · π >> ο ί> >> I ι IIII · ΡΡΡ £ Τ -μ £ -Γ)

ScmcmcmcmojcmcmCCC oj en C

PI I I I I I I Ό Ό Ό CliC'O

<D * 1-1 -r- * rT T * «-r * r-l T- * Q) -r * 3 ID (Q u) • Hcnwwwwwwxxix: e to w e h, 2

Μ555Ι5555τηΪ! Τ · · ρ ^ r Q

^ COOOOOOOr ^ rl ^ CO. — ι c -μ 3 2 5 5 3 5 5 5 5 5 ¾¾ 83 δΙΐ3 ρχίοοχχβχ-Ρ-Ρ-Ρ π5ί? Η f ^ cöncncnrörocö iii <muQwfaIe3Xtxo, D5 -ι cm co q- m to

8 6 6 4 G

11

Examples 1-6 Samples 1-6 were simple tiling cement mortars used as laboratory standards. This cement-mortar was a mixture of 350 parts by mass of Portland cement, 650 parts of sand and 5 parts of a thickener (polyacrylamide refractile ether was used instead of the cellulose ether part in symbols 3, 4 and 5). The thickener was the cellulose ether of Table 1 or a mixture of such cellulose ether and starch ether or polyacrylamide.

Tile cement mortar. the Hobart N50 mixer described in DIN 1164, Part 7 was used for mixing.

Slab cement mortar was manufactured in accordance with DIN 18156, part 2. Dry cement mortar was prepared by mixing 174.1 g of Portland cement C, 323.4 g of sand M 34 (0.1-0.2 mm) and 2.5 g of cellulose ether (Polyacrylamide or starch ether was used in place of the cellulose ether portion in the examples in a 1.5 liter plastic bag). 3, 4 and 5) and the resulting mixture was shaken for 3 minutes. Water was poured into the Hobart mixer in the amounts indicated in Table 2. Dry cement mortar was then gradually added to the water and mixing was continued after the addition in the vessel at low speed for 30 seconds.

The blade of the Hobart mixer was then removed, the mortar adhering to the blade was scraped off and put back into the mixture and the blade was reattached, all these steps in 30 seconds, and the mortar was mixed for another 30 seconds.

The amount of water used was chosen to optimize the appearance and consistency.

The formulations are shown in Table 2.

86640 12 Γ “· • σ LT) ρ ρ

OJ g P

ρ ·> »rt p O O O I I I t lO I I O p rt d, in i / i ρ rt

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P rt O P

r-1 g rt O

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P g p> iC P

tn p £ o tn rt · * -n, α • —i: o O C rt rt tn • ri p in in co ·· rt ·· -> p

P C «** 2 ^ P

p -p o o i co i i i i p o Tl rt * S

Ccotnmm> 150 S

δ x co to tn rt ag rt 00 po rt 2 oj tn tn u tn —- rt -pa • P ry rt E 'f-1 V ^ tn E tn p tn ζ: oo E ρ £ 2 rt p oj -pe -PO

V e - z. o o C

e -ι-i o o 1 tn 1 1 1 1 1 O ρ 10 Ό rtojtnmm tn e >>>! p 2 co m in ro px: en rt wo 1 gp „pe rt p '1 — I" "O rt' - * oj oo >> ep in n ρ <υ om tn u rt 2 r— oj 2 · Η e 5 o, 2 co * "5 <—1 · · rt rt tn 3 £ oom 1 1 1 1 1 1 o ---) 0 ^ ρ ρ pf — tp S mm rt 1 o —1 e rt g co to Prt -Pgrtrt rt S tn rt 1—1 rt a E-ι '-rp rt o rt p P tn δ x tn e tn p E e! Rt rt • peop tn eoo Ό rt tn rt p tn cu rt ^ ci ro tfl Cp pypy Jj CÖ P PM Π3 rt ge 2 p rt tn p CE oep js; rt in rt • '-iee XE e rt CO' -s X Sh -p rt C "* U: rt 5 * r- * *" Cu 4- * .Cy Cu CJ T <CQ D IX O tj- PpP Pp> I p rt P Ό pPp rt -P «p 01 co Ό e · ρ tn · >> rt p> POL · pp £ 92 g 3 SS> Ä PP p- <D TJtyrt F rt rt rt D.

rt e p ptutn © p tn £ o rt rt

X rt rt g 4 »P <0 P p E P p P

tn g 2 <l> rt p tn 1>. C Cu tn tn

Oj- 552 rt Prtrt 'USOQpoo rt rt tnturt prt> CP-pQtn tn r iPtn b ^ tn <3 xe rt x · tn ό .eo? >>>>> pcöroojprt C Cp O CpP P t >> m Ό rt rt 10 P 2 rt PCHS · Ρ Ή £ tn pprt rt 2 rt ooop >> rt M pe P >> 3 P a, pu, tn o fr en rt U rt PPC> 1 EO> rt o .rt: rt · · · · P-Oy ^ tn Oy H g POJ 00 ^ i3 86640

The appearance, formability, consistency, tack, and water separation of the final paste were evaluated visually and by hand mixing. Landing resistance using a heavy slab, open time and adhesion were measured as follows.

Landing resistance using heavy slab

The adhesive was applied to a horizontal concrete base by grooving into rectangular teeth (6x6x6 mm) with a trowel. The fixative was allowed to stand for 10 minutes, after which an unabsorbed plate measuring 150 x 150 x 11 mm (about 585 g) was placed on top of the fixative and a pressure of 5 kg was applied for 30 seconds. The original location at the top of the tile was marked. The concrete slab was then carefully placed in a vertical position. After about 30 minutes, the location of the top of the tile was marked and the distance between the two marks was measured to find out how much the tile had slipped.

open time

The open time was measured according to DIN 18156, but the tiles described below were used. The adhesive was applied to the horizontal concrete as described above for the determination of the settling resistance. After 5, 10, 15, 20, 25 and 30 minutes, respectively, an absorbent plate (50 x 50 mm) was placed on top of the adhesive and a pressure of 0.5 kg was applied for 30 seconds. After 30 minutes, the tile was removed and it was observed how much mortar was attached to the tile. The time after which the adhesive residue decreased sharply was considered the open time of the tile cement mortar.

Determination of adhesion

The adhesive was applied to the bottom in the same manner as described above for the determination of the settling resistance 14 86640. After 10 minutes, 6 absorbent plates measuring 50 x 50 mm were placed on top of the adhesive and a pressure of 2 kg was applied for 30 seconds. The tiles were allowed to set and then stored horizontally at 23 ° C and 50% relative humidity. After 1 day and 7 days, 3 bricks were pulled off, respectively, with a Sattec attachment tester, a hydraulic traction device. In this experiment, a metal plate with a diameter of 5.0 cm with a screw hole in the center for attachment to the test apparatus was placed on the tiles, the tiles were pulled off, and the adhesion was measured.

The results obtained are shown in Table 3.

15 86640

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Table 3 shows the improvement in results obtained using the 3-butoxy-2-hydroxypropylhydroxyethylcellulose of this invention. Compared to methylcellulose, the cellulose ether of this invention provides better moldability, higher settling resistance, longer open time with a higher percentage of water content, and approximately the same adhesion.

When starch ether is mixed in, the opening time is even longer because the amount of water can be increased, which also improves the consistency. Landing resistance is still excellent. When combined with polyacrylamide, the hydroxyethylcellulose of this invention behaved as well as methylcellulose. However, the opening time was longer because a larger amount of water could be added.

Examples 7-12 These examples are intended to compare U.S. tile cement mortar formulations having the 3-butoxy-2-hydroxypropylhydroxyethylcellulose of this invention to those having hydroxypropylhydroxyethylcellulose or hydroxypropylmethylcellulose.

Samples 7-12 were prepared by placing the dry ingredients, i.e., Portland cement, sand, and thickener (in some examples, polyacrylamide in place of the cellulose ether portion) listed in Table 4 in a container, sealing the container, and shaking it. The desired amount of water was then placed in a mixing tank and the dry mixture was added. The cement mortar was then mixed with a mixing stick for about 1 minute to obtain a homogeneous consistency. Before testing the cement mortar, it was allowed to go out for 15 minutes.

The results obtained are shown in Table 4.

1 7

8 6 6 4 O

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r-v 00 C \ J CM

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a> -p -p ό «E E

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18 B 6 6 4 O

Formability was assessed visually and by hand mixing. Landing resistance, peeling resistance and strength were measured as follows.

The descent Resistance

A layer of cement mortar was cast on a wallboard between two 3 mm (1/8 inch) metal bars and an unabsorbed tile (size 10.16 x 10.16 cm; 4x4 inches; weight 200 g) was pressed over the layer. A line was drawn on the cement mortar at the top of the slab and the board was placed in a vertical position. After a certain time, the landing distance was measured from the line to the top of the slab. If the distance is more than 1.59 mm (1/16 inch), the cement mortar has been too wet, so less water should have been added. If no settling is observed at all, the cement mortar has been too dry, so more water should have been used. The optimal amount of water gives the slab a descent distance of 0.79 mm to 1.59 mm (1/32 to 1/16 inch).

Kuorettumisenvastustuskyky

A layer of cement mortar was applied to the wallboard with a masonry trowel with 6.35 x 6.35 mm (1/4 x 1/4 inch) notches. Immediately after application, an absorbent tile (5.08 x 5.08 cm; 2x2 inches) was placed on top of the cement mortar and a weight of 1 kg was placed on the tile. After 5 minutes, another similar tile was placed on another area of applied cement and held in place under a weight of 1 kg. The first slab was pulled off by hand and the area of the cement mortar covering the surface was evaluated. After a further 5 minutes, a third brick was placed in the third area of the applied cement mortar and the second brick was pulled out and the cement-mortar area covering the surface was evaluated. Five minutes later, the third tile was finally pulled off.

19 "6640 This test shows the thickener's resistance to" peeling ". The greater the amount of cement mortar covering the tiles, the greater the tendency of the cement mortar to adhere to the surface. The values of the first tile (called 0-time surface adhesion) are normally 90 The values of the second plate (5 min SA) are normally between 27 and 75% and the values of the third plate are typically between 0 and 25%.

shear strength

Shear strength, i.e., average strength after one day, was measured as follows. 11.43 x 11.43 cm (4 1/2 x 4 1/2 inches) was cut in the middle and cemented together with 3.175 mm (1/8 inch) tile cement mortar 2 layers (area 412.8 cm; 64 square inches). The cement mortar was allowed to dry for 24 hours at 21.1 ° C (70 ° F) at 50% relative humidity. A vertical force was then applied at a constant speed and the load was recorded.

The results obtained are shown in Table 5.

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Tables 4 and 5 show two sets of different cement mortars with different water ratios. In the first series (Examples 7-9), the mixture according to the invention (without additive) worked in the same way as the MHPC sample with additive. In another series (Examples 10-12), the mixture of this invention (without additive) showed much better peel resistance than MHPC (with additive included). Better peel resistance allows for more efficient design. The present invention provided excellent formability in both series.

This superiority manifested itself in greater smoothness when applied with a spatula and as sharpness in the cement mortar layer when grooved.

Examples 13-15 These examples represent a comparison of cement blocks. A cement block is a mixture of cement, sand and light gravel that is applied by spraying into suitable parts of buildings.

The formulation used in these examples, in which all parts are based on mass, is shown in Table 6.

22 86640

Table 6

Massa Pieces

Aineosa_ (dry blended)

Portland Cement A '180

Lime (95%) 50

Quartz sand (0.05-2 mm) 2 740

Vermiculite 20 AL-si1i was poured 10

Total amount of spolymer (cellulose ether and polyacrylamide) 1.6 1. Standard Portland cement with a compressive strength of 35 N / mm2 after 8 days 2. Quartz sand mixture with 1 part by mass of 1-2 mm, 2 parts by weight of fraction 0 , 1-1.0 mm and 1.5 parts by mass of fraction 0.05-0.3 mm.

23 866: 0

A dry cement plug having the above composition was added at 500 rpm with stirring to water to achieve the ratio shown in Table 7. After the addition, stirring was continued for 15 or 30 seconds at 800 rpm as needed to obtain a homogeneous mixture.

Appearance and formability were determined visually and by hand mixing. Water separation, air content and application value were measured as follows.

Water Separation This test shows the amount of water loss or water separated that occurs in a composition when in contact with an absorbent surface. The very high water separation may result in low strength of the dry stucco and cracking of the stucco, which is why a low water separation value is desirable.

Water separation was measured by first stacking 10 40 Whatman filter paper rings (diameter 9.0 cm; filtration rate according to ASTM D981-65 in 100 ml of water in 75 seconds; mass 95 g / m; thickness 0.20 mm) and then the stack was weighed. The stack of filter paper was then placed on a flat surface and covered with an 11.0 cm no. 54 Whatman filter paper (filtration rate 100 ml water per 10 seconds according to ASTM D981-56). A cylinder with a diameter of 5.08 cm (2 inches) and a length of 7.62 cm (3 inches) was placed on top of this stack of filter paper. The cylinder was filled to the brim with wet mortar mixture. After 1 minute, the cylinder and top filter paper were removed. The stack of filter paper was weighed to determine the amount of water absorbed, expressed as the amount of water separated from the mortar mixture in grams (g) · 8 6 6 40 24

air Concentration

The amount of water retained in the mixture was determined gravimetrically. The wet, sprayable mortar mixture was placed in a cylinder of known volume and tapped lightly 100 times to remove any large air bubbles. A piece was sawn off from the top of the cylinder to obtain a known amount of mixture by volume. The resulting mixture was weighed. When the specific gravity of the wet mixture and the specific gravity of the dry matter of the mixture were known, the air volume of the wet mixture could be calculated. The high air content results in a smoother and creamier consistency and is therefore desirable.

Application value

The application value or flowability was measured with a Hagerman flow table according to DIN 1060 / DIN 18555 (which flow table is similar to that described in ASTM c230-68T). the table was dropped through a height of 1 cm 15 times.

Ruiskutuskoe

The dry mixture, the formulation of which is shown in Table 6, was poured into the tank of a Putzmeister Gipsomat G78 sprayer, from where it was introduced into the mixing chamber. The mixing chamber was connected to a water tap. The dry mixture was then mixed with water and transferred by a screw pump to a 10 meter hose and sprayed through a nozzle at the end of the hose onto the wall surface. The time between the first water contact and the exit of the hose from the nozzle was 17 to 20 seconds. Over the next 1-2 hours, successive application and finishing treatments were performed to obtain a uniform result.

25 86640

Table 7 - Cement block 13 14 15

Observed Feature_ (MHEC) (Invention) (Invention)

Laboratory okokeet water ratio1 0.265 0.265 0.265 cellulose ether R (parts) 1.52 F (parts) - 1.6 G (parts) - - 1.6 polyacrylamide (parts) 0.08

Appearance smooth smooth smooth

Formability good excellent excellent property

Application area (cm) 15.5 15.5 15.5

Paste density (g / cm 2) 1.48 1.44 1.45

Air content paste density after 5 min 1.50 1.45 1.47 after 15 min 1.50 1.48 1.47 after 30 min 1.51 1.49 1.47

Flexural strength (N / W) 1.7 1.8 1,

Squeeze strength (N / rrni3) 4.7 4.7 4.8

Weather (%) 20 22 21

Separation of water (mg after 3 min) 2505 2325 2432. -. Application tests ~ stucco / water ratioJ 3.6 3.3 3.3 spraying behavior good / excellent excellent excellent specific water flow (1 / h) 335 350 350 pressure (bar) 20 19-20 19 cracking no law no law - Not at all

Amount of water added (by weight) / amount of dry stucco (by weight) 2

Amount of dry stucco (by weight) / amount of water (by weight) 3

Non-ionized polyacrylamide, 1% solution 800 mPa 26 86640

The results of Table 7 show that the polymers of this invention improve formability and water retention. The latter property is advantageous when using highly absorbent surfaces. Higher potential water flow in large-scale experiments improves cement block yields and thus lowers costs.

Examples 16 to 18 These examples are intended for comparison with sprayable gypsum mortars. The formulation used in this example is shown in Table 8, where all parts are mass parts. Samples were prepared by adding polymers (cellulose ether and polyacrylamide), an air retention agent, and a binder to a finished mixture of gypsum, anhydride, and hydrated lime. The samples were evaluated as described in Examples 13-15.

Table 8

Ingredient Parts ^

Gypsum (CaSO 4 1/2 H 2 O) 500

Anhydride II 450

Hydrated lime. 50

Total polymer content (cellulose ether and polyacrylamide, see Table 9)

Air retardant (sodium lauryl sulphate) see Table 9

Binding retardant (citric acid) 0.5 1. Parts are based on the total amount of mixture without water.

27 8 6 6 4 Π

Table 9 - Sprayable gypsum mortar 16 17 18

Detected Feature_ (MHEC) _Invention_ (Invention)

Gypsum mortar / water ratio ^ 1.9 1.9 1.9

Cellulose ether R (parts) 1.51 F (parts) - 1.45 G (parts) - - 1.46

Polyacrylamide (parts) ^ 0.08 0.08 0.08 3

Retention pressure (parts)

Appearance smooth smooth smooth

Formability good excellent excellent

Application value (cm) 16.7 16.3 15.9

Paste density (g / cm 3) 1.61 1.59 1.60

Air content (%)

Water separation (rrg after 9 minutes) 2210 1345 2915 1. Gypsum mortar (by mass) / added water (by mass) 2. Non-ionized polyacrylamide with a viscosity of 00 mPas in a 1% solution.

3. Sodium lauryl sulfate? Ö 86640

The above results show that the invention provides excellent moldability for sprayable mortars. All other properties except water separation were similar. The best water separation value was obtained with cellulose ether F, which had a higher degree of 3-butoxy-2-hydroxypropyl substitution than cellulose ether G, indicating the importance of hydrophobicity.

Examples 19 - 21 These examples concern the comparison of gluing plasters. Bonding gypsums are very pure, finely divided gypsum and are used for gluing gypsum pieces together. The formulations are shown in Table 10.

Appearance and consistency were measured visually. Flexural strength and compressive strength were measured in accordance with ASTM C348 and ASTM C108-80, respectively. The adhesion force was measured after 7 days as described in Examples 1 to 6. The metal disc was glued to an annular area 5 cm in diameter made with a hollow cutter on the surface of the gypsum body with an adhesive layer.

The results obtained are shown in Table 10 below.

6 6 6 ·: O

29

Table 10 - Gluing plaster

Observed 19 20 21 property (HEHPC) (Invention) (MHEC)

Gypsum (CaSO 4 1/2 H 2 O) (parts) 1 1000 1000 1000

Cellulose ether A (parts) 1 1 - H (parts) 1 - 0.8 R (parts) 1 - - 1.2 1 2

Binding retardant (s) '0.1 0.1 0.1 Water ratio used2 0.68 0.68 0.68

Appearance of lumps smooth smooth

Consistency weak solid solid

Flexural strength (N / mm2) - 3.7 3.6

Compressive strength (N / mm2) - 8.9 8.3

Adhesion strength (N / cm2) - 46.84 46.84 1. Parts measured on the basis of the total mass of the mixture, without water 2. Formic acid 3. Amount of water added (by mass) / volume of the mixture (by mass of persute) (without added water) 4. Platform breakage

The sample of the present invention had better appearance and consistency compared to the corresponding properties of sample 19 (HEHPC), and the strength of the sample of the invention was very much better even though cellulose ether was present at a lower concentration.

86640 30

Example 22 This example represents the preparation of a grout using 3-butoxy-2-hydroxypropylhydroxyethylcellulose of the present invention. The formulation of the sample is shown in Table 10. Limestone, clay, mica and cellulose ether were placed in a vessel and mixed together. The water was placed in a Hobart N50 mixer. A binder was added to the water and mixed. The dry mixture was then added to the liquid dispersion obtained above and stirred mechanically for 20 minutes.

Appearance was rated on a subjective rating scale of 1-5. A rating of 1 means that the sample is very smooth and creamy. A rating of 5 means that there is a very high degree of granularity.

Jelly was measured subjectively. Jelly-free means putty of elastic properties ("texture"), while strong jelly-like means that the paste is similar to cooked starch jelly.

Table 11 - Joint mortar

Example 22 (invention)

Limestone (mass%) 58.6

Attapulgite clay (mass%) 2.0 2

Binder 1.5

Mica (mass%) 3.0

Cellulose ether F (% by weight) 0.4

Water (wt%) 34.5

Viscosity (BU) ^ 600

Appearance 1

Jelly very low 1. Viscosity according to ASTM C474-67.

2. A polyvinyl acetate emulsion internally plasticized with 10% dibutyl phthalate sold under the trademark Ucar 131 (Union Carbide Corporation).

31 866 40

The appearance was excellent, but the gelation was very low.

The alkyl glycidyl-derived radical-containing polymers of this invention are, as mentioned above, useful as stabilizers in emulsion polymerization, as protective colloids in suspension polymerization, as thickeners in cosmetics and shampoos, and as flocculants in mineral processing.

Claims (11)

1. Water-soluble cellulose derivative, the first substituent of which has been selected from hydroxyethyl, hydroxypropyl and methyl, characterized in that this cellulose derivative is also substituted by ca. 0.05 - approx. 50%, due to the dry mass of substituted cellulose derivative calculated, of a 3-alkoxy-2-hydroxypropyl group, the alkyl of which is a branched or branched alkyl group of 2-8 carbon atoms. A water-soluble cellulose derivative according to claim 1, characterized in that the amount of the 3-alkoxy-2-hydroxypropyl group is approx. 0.1 - approx. 25% by mass. Water-soluble cellulose derivative according to claim 1 or 2, characterized in that the alkyl moiety consists of an unbranched alkyl group having 2-6 carbon atoms. Water-soluble cellulose derivative according to claim 1, 2 or 3, characterized in that the 3-alkoxy-2-hydroxypropyl group is a 3-butoxy-2-hydroxy-propyl group. Water-soluble cellulose derivative according to any preceding claim, characterized in that the first substituent is hydroxyethyl and that the cellulose derivative is ionized. Water-soluble cellulose derivative according to claim 4, characterized in that the molar hydroxyethyl substituent degree is about 1.5 - 3.5. Water-soluble cellulose derivative according to any of the preceding claims, characterized by its degree of polymerization is approx. 1500 - approx. 4000th Building material mixture containing hydraulic or synthetic binder, characterized in that this mixture also contains approx. 0.5 - approx. 5% by mass of water-soluble cellulose derivative according to the preceding claim. 9. Building material mixture according to claim 8, characterized in that the binder consists of portland cement or building plaster. Building material mixture according to claim 8, characterized in that the binder consists of a synthetic binder which is polyvinyl acetate homopolymer or ethylene-polyvinyl acetate copolymer. 11. Building material mixture, characterized in that it contains filling material, which can be selected from the group consisting of gravel, sand, dolomite, gypsum, limestone, perlite, vermiculite and polystyrene.